CN109789957B

CN109789957B - Flexible fitting for flexible container

Info

Publication number: CN109789957B
Application number: CN201780056041.4A
Authority: CN
Inventors: 马良凯; S·L·卡佩瑞; J·C·戈梅斯; M·H·米尔戈贡; M·S·布莱克; M·O·拉博内维尔; M·J·特平; M·J·希思; C·M·塞勒; L·A·万舒姆雷恩; N·C·马佐拉
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2016-09-26
Filing date: 2017-09-25
Publication date: 2021-02-12
Anticipated expiration: 2037-09-25
Also published as: JP7050764B2; US20180086527A1; MX2019002808A; EP3515835A1; BR112019004796A2; CN109789957A; CO2019003610A2; ES2837762T3; AR109542A1; US10173821B2; TW201819259A; EP3515835B1; WO2018058047A1; JP2019530616A; TWI746640B

Abstract

The present disclosure provides a flexible container. In one embodiment, the flexible container (8) includes a first multilayer film (16) and a second multilayer film (18). Each multilayer film includes a seal layer. The multilayer films are arranged in such a way that the seal layers are opposite to each other and the second multilayer film (18) is superimposed on the first multilayer film (16). The multilayer films are sealed along a common peripheral edge (20). The flexible container (8) comprises a fitment (10). The fitting (10) includes a substrate (12). The substrate (12) comprises a polymeric blend of 60 to 90 weight percent of an ethylene/alpha-olefin multi-block copolymer and 40 to 10 weight percent of a High Density Polyethylene (HDPE). The flexible container (8) includes a fitment seal (22), the fitment seal (22) including the substrate (12) positioned between the multilayer films. The substrate (12) is sealed to each multilayer film at a portion of the common peripheral edge (20).

Description

Flexible fitting for flexible container

Background

The present disclosure relates to a flexible container having a flexible fitment.

Flexible pouches having rigid pour spouts for storing and delivering flowable materials are known, and are commonly referred to as "pour pouches". Many conventional pouring bags utilize a rigid pouring spout, wherein the base of the spout has winglets. Each winglet is a structure perpendicular to the base, each winglet extending radially away (in opposite directions) from the annular base of the spout. The winglets are used to increase the surface area of the annular base to promote adhesion between the spout and the flexible packaging film.

Winglets are problematic, however, because they require special heat sealing bars to effectively seal the winglets to the flexible film package. Specialized heat seal strips require unique shapes that match the shape of the spout base and winglet. In addition, the heat sealing process requires precise and matching alignment between the spout and the film to ensure that the spout is aligned parallel to the film orientation.

As a result, the production of flexible bags is filled with inefficiencies due to (1) the expense of specialized heat sealing equipment, (2) production downtime for precise seal-winglet alignment, (3) production downtime required for precise spout-film alignment, (4) failure rates (leakage) due to misalignment, and (5) quality control steps required at each stage of the pouring bag production.

The art recognizes the need for alternative methods of producing pouring bags. The art further recognizes the need for an improved pouring spout that avoids the production disadvantages of spouts with winglets.

Disclosure of Invention

The present disclosure provides a flexible container. In an embodiment, the flexible container includes a first multilayer film and a second multilayer film. Each multilayer film includes a seal layer. The multilayer films are arranged in such a manner that the seal layers are opposed to each other and the second multilayer film is superimposed on the first multilayer film. The multilayer films are sealed along a common peripheral edge. The flexible container includes a fitment. The fitment includes a substrate. The substrate comprises a polymeric blend of 60 to 90 weight percent of an ethylene/alpha-olefin multi-block copolymer and 40 to 10 weight percent of a High Density Polyethylene (HDPE). A flexible container includes a fitment seal comprising the substrate positioned between the multilayer films. The substrate is sealed to each multilayer film at a portion of the common peripheral edge.

Drawings

Fig. 1 is a perspective view of a flexible container according to an embodiment of the present disclosure.

Fig. 1A is an enlarged view of region a of fig. 1, in an embodiment of the present disclosure, a flexible container having a closure.

Fig. 1B is a perspective view of the flexible container of fig. 1 with a closure according to an embodiment of the present disclosure.

Fig. 2 is an enlarged view of the area a of fig. 1.

Fig. 3 is a cross-sectional view of the bag of fig. 1 taken along line 3-3 of fig. 2.

Fig. 4 is a bottom plan view of the flexible container of fig. 1.

Fig. 5 is a top plan view of the flexible container of fig. 1.

Definition of

All references herein to the periodic table of elements shall refer to the periodic table of elements published and copyrighted by CRC Press, Inc. Further, any reference to one or more of the groups shall be to any reference to one or more of the groups reflected in this periodic table of elements using the IUPAC system to number the groups. All parts and percentages are by weight unless stated to the contrary, implied by the context or by convention in the art. For purposes of united states patent practice, the contents of any patent, patent application, or publication referred to herein are incorporated by reference in their entirety (or the equivalent us version thereof is so incorporated by reference), especially with respect to the disclosure of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge in the art.

The numerical ranges disclosed herein include all values between and including the lower and upper values. For ranges containing exact values (e.g., 1 or 2, or 3 to 5, or 6, or 7), any subrange between any two exact values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.).

Unless stated to the contrary, implied by context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

As used herein, the term "composition" refers to a mixture of materials comprising the composition and reaction and decomposition products formed from the materials of the composition.

The terms "comprises," "comprising," "includes," "including," "has," "having" and derivatives thereof, whether or not the component, step or procedure is specifically disclosed, are not intended to exclude the presence of any additional component, step or procedure. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise. Conversely, the term "consisting essentially of … …" excludes any other components, steps, or procedures from any subsequently recited range except those not essential to operability. The term "consisting of … …" excludes any component, step, or procedure not specifically recited or recited.

Density is measured in accordance with ASTM D792, where values are reported in grams per cubic centimeter (g/cc).

Elastic recovery is measured as follows. Using an Instron at 21 deg.C^TMGeneral purpose tester at 300% minute^-1The deformation ratio measures the stress-strain characteristic in uniaxial tension. After loading to 300% strain using ASTM D1708 micro tensile specimensThe load and unload cycle was measured for 300% elastic recovery. Percent recovery was calculated for all experiments after an unloading cycle using strain to return loading to baseline. Percent recovery is defined as:

recovery% (% Ef-Es)/Ef

Where Ef is the strain employed for cyclic loading and Es is the strain loaded back to baseline after the unloading cycle.

Elongation at break and tensile modulus were each measured according to ASTM D638. Elongation at break is the strain at which the sample breaks. The value of elongation at break is expressed in percent (%). Values for tensile modulus are reported in megapascals (MPa). ASTM D638 test procedure requires the use of a nominal type IV dog bone specimen cut from an extruded strip having a nominal 0.50mm thickness. Tensile test in

The tensile tester was run at a test speed of 20 inches/minute.

An "ethylene-based polymer" is a polymer that contains more than 50 weight percent polymerized ethylene monomer (based on the total weight of polymerizable monomers) and optionally may contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymer" and "polyethylene" are used interchangeably. Non-limiting examples of ethylene-based polymers (polyethylenes) include Low Density Polyethylene (LDPE) and linear polyethylenes. Non-limiting examples of linear polyethylenes include Linear Low Density Polyethylene (LLDPE), Ultra Low Density Polyethylene (ULDPE), Very Low Density Polyethylene (VLDPE), multicomponent ethylene copolymers (EPE), ethylene/alpha-olefin multi-block copolymers (also known as Olefin Block Copolymers (OBC)), single site catalyzed linear low density polyethylene (m-LLDPE), substantially linear or linear plastomers/elastomers, and High Density Polyethylene (HDPE). Generally, polyethylene can be produced in a gas phase fluidized bed reactor, a liquid phase slurry process reactor, or a liquid phase solution process reactor using a heterogeneous catalyst system (e.g., Ziegler-Natta catalyst), a homogeneous catalyst system comprising a group 4 transition metal and a ligand structure (e.g., metallocene, non-metallocene metal-centered heteroaryl, isovalent aryloxyether, phosphinimine, etc.). Combinations of heterogeneous and/or homogeneous catalysts may also be used in a single reactor or dual reactor configuration.

"Low density polyethylene" (or "LDPE") consisting of a homopolymer of ethylene having a density of from 0.915g/cc to 0.940g/cc and containing long chain branches with broad MWD or comprising at least one C₃-C₁₀Alpha-olefins, preferably C₃-C₄Of an ethylene/alpha-olefin copolymer. LDPE is usually produced by means of high pressure free radical polymerization (tubular reactor or autoclave with free radical initiator). Non-limiting examples of LDPE include MarFlex^TM(Chevron Phillips), LUPOLEN^TM(LyondellBasell) and LDPE products from northern Europe chemical industry (Borealis), Enlishi (Ineos), Exxon Mobil (ExxonMobil), etc.

A "linear low density polyethylene" (or "LLDPE") is a polyethylene comprising units derived from ethylene and units derived from at least one C₃-C₁₀Alpha-olefin comonomer, or at least one C₄-C₈Alpha-olefin comonomer, or at least one C₆-C₈Linear ethylene/alpha-olefin copolymers containing heterogeneous short chain branching distribution of the units of the alpha-olefin comonomer. LLDPE is characterized by little, if any, long chain branching compared to conventional LDPE. The LLDPE has a density of 0.910g/cc, or 0.915g/cc, or 0.920g/cc, or 0.925g/cc to 0.930g/cc, or 0.935g/cc, or 0.940 g/cc. Non-limiting examples of LLDPE include TUFLIN^TMLinear Low Density polyethylene resin (available from The Dow Chemical Company), DOWLEX^TMPolyethylene resin (available from Dow chemical) and MARLEX^TMPolyethylene (available from cheffoniphil).

"ultra-low density polyethylene" (or "ULDPE") and "very low density polyethylene" (or "VLDPE") are each a polyethylene composition comprising units derived from ethylene and derived from at least one C₃-C₁₀Alpha-olefin comonomer, or at least one C₄-C₈Alpha-olefin comonomer, or at least one C₆-C₈Linear ethylene/alpha-olefin copolymers containing heterogeneous short chain branching distribution of the units of the alpha-olefin comonomer. The densities of ULDPE and VLDPE are each 0.885g/cc or 0.90g/cc to 0.915 g/cc. Non-limiting examples of ULDPE and VLDPE include ATTANE^TMUltra low density polyethylene resin (available from Dow chemical) and FLEXOMER^TMVery low density polyethylene resins (available from the dow chemical company).

"multicomponent ethylene-based copolymer" (or "EPE") comprising units derived from ethylene and units derived from at least one C₃-C₁₀Alpha-olefin comonomer, or at least one C₄-C₈Alpha-olefin comonomer, or at least one C₆-C₈Units of alpha-olefin comonomers are described, for example, in the patent references USP 6,111,023, USP 5,677,383 and USP 6,984,695. The EPE resin has a density of 0.905g/cc, or 0.908g/cc, or 0.912g/cc, or 0.920g/cc to 0.926g/cc, or 0.929g/cc, or 0.940g/cc, or 0.962 g/cc. Non-limiting examples of EPE resins include ELITE^TMReinforced polyethylene (available from Dow chemical Co.), ELITEAT^TMAdvanced technology resins (available from the Dow chemical company), SURPASS^TMPolyethylene (PE) resins (available from Norwalk Chemicals) and SMART^TM(available from fresh Jing chemical Co., Ltd.).

A "single-site catalyzed linear low density polyethylene" (or "m-LLDPE") is a polyethylene comprising units derived from ethylene and units derived from at least one C₃-C₁₀Alpha-olefin comonomer, or at least one C₄-C₈Alpha-olefin comonomer, or at least one C₆-C₈Linear ethylene/alpha-olefin copolymers containing a homogeneous short chain branching distribution of units of the alpha-olefin comonomer. The m-LLDPE has a density of 0.913g/cc, or 0.918g/cc, or 0.920g/cc to 0.925g/cc, or 0.940 g/cc. Non-limiting examples of m-LLDPE include EXCEED^TMMetallocene PE (available from ExxonMobil Chemical), LUFLEXEN^TMm-LLDPE (commercially available from RiandBarcel) and ELTEX^TMPF m-LLDPE (commercially available from Enlishi Olefins and polymers (Ineos Olefins)&Polymers))。

An "ethylene plastomer/elastomer" is a polymer comprising units derived from ethylene and derived from at least one C₃-C₁₀Alpha-olefin comonomer, or at least one C₄-C₈Alpha-olefin comonomer, or at least one C₆-C₈Substantially linear or linear ethylene/alpha-olefin copolymers containing a homogeneous short chain branching distribution of the units of the alpha-olefin comonomer. The ethylene plastomer/elastomer has a density of 0.870g/cc, or 0.880g/cc, or 0.890g/cc to 0.900g/cc, or 0.902g/cc, or 0.904g/cc, or 0.909g/cc, or 0.910g/cc, or 0.917 g/cc. Non-limiting examples of ethylene plastomers/elastomers include AFFINITY^TMPlastomers and elastomers (available from Dow chemical Co., Ltd.), EXACT^TMPlastomers (available from exxon Mobil chemistry), Tafmer^TM(commercially available from Mitsui), Nexlene^TM(available from Xinjin chemical Co.) and Lucene^TM(available from LEJIN Chemicals, Inc. (LG Chem Ltd.)).

A three detector gel permeation chromatography or GPC (3D-GPC or TDGPC) system was used, consisting of a Polymer laboratory (now Agilent) high temperature chromatograph 220 model equipped with a 2-angle laser Light Scattering (LS) detector 2040 model (precision detector, now Agilent), an IR-4 infrared detector from Polymer Char (Valencia, Spain), and a 4 capillary solution viscometer (DP) (wiskott corporation (Viscotek), now marvens (Malvern)). Data collection was performed using Polymer Char DM 100 data collection box and related software (balncian, spain). The system was also equipped with an on-line solvent degassing unit from the polymer laboratory (now agilent). High temperature GPC columns consisting of four 30cm, 20 μm mixed a LS columns from the polymer laboratory (now agilent) were used. The sample transfer chamber was operated at 140 ℃ and the column chamber was operated at 150 ℃. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and sample preparation solvent was 1,2, 4-Trichlorobenzene (TCB) containing 200ppm of 2, 6-di-tert-butyl-4-methylphenol (BHT). The solvent was sparged with nitrogen. The polymer sample was gently stirred at 160 ℃ for four hours. The injection volume was 200 microliters. The flow rate through GPC was set at 1.0 ml/min. Use ofPolymer Char "GPC One" software for column calibration and sample molecular weight calculation. Calibration of the GPC column was performed using 21 narrow molecular weight distribution polystyrene standards. Polystyrene standards have molecular weights of 580 to 8,400,000g/mol and are arranged in 6 "cocktail" mixtures at least ten times apart between the individual molecular weights. The peak molecular weight of Polystyrene standards was converted to Polyethylene molecular weight Using The following equation (as described in T.Williams and I.M.Ward, Construction of Polyethylene Calibration curves for Gel Permeation Chromatography Using Polystyrene Fractions (The Construction of a Polyethylene Calibration Curve for Gel Permeation Chromatography), 6J.Polymer Sci.Pt.B: Polymer Letter 621,621-624 (1968)): m_Polyethylene＝A(M_Polyethylene)^B. Here, the value of B is 1.0, and the experimentally determined value of a is about 0.38 to 0.44 the column calibration curve was obtained by fitting the first-order multi-top version of the corresponding polyethylene equivalent calibration points obtained from the above equation to the observed elution volume values. The conventional number and weight average molecular weights (mn (conv) and mw (conv), respectively) were calculated according to the following equations:

wherein, Wf_iIs the weight fraction of the ith component, and M_iIs the molecular weight of the ith component. The Molecular Weight Distribution (MWD) is expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The A value was determined as follows: the a values in Williams and wald equations (the Williams and Ward's Equation) are adjusted until the weight average molecular weight Mw calculated using the above equations and the corresponding hold-up volume polynomials corresponds to an independent measure of Mw obtained from a linear polyethylene homopolymer reference having a known absolute weight average molecular weight of 115,000g/mol, as measured according to LALLS in the manner of a traceable standard homopolymer polyethylene NBS 1475. The absolute weight average molecular weight (Mw (abs)) is characterized by the LS detector and the IR-4 concentration detector using the following equations:

where ∑ (LS)_i) Is the response area of the LS detector, Σ (IR)_i) Is the response region of the IR-4 detector, and K_LSIs an instrument constant, determined using a standard NIST 1475 with known concentration and assay values of weight average molecular weight of 52,000 g/mol. The absolute molecular weight at each elution volume was calculated using the following equation:

wherein K_LSIs the measured instrument constant, LS_iAnd IR_iIs the LS and IR detector response of the same ith elution fraction. The absolute number average molecular weight and the ξ -average molecular weight are calculated using the following equations:

when log M_LS,iData scatter at log M due to low LS or IR detector response_LS,iLinear extrapolation on elution volume plot.

Melt Flow Rate (MFR) is measured according to ASTM D1238, condition 280 ℃/2.16 kg (g/10 min).

Melt Index (MI) is measured according to ASTM D1238, condition 190 ℃/2.16 kilogram (g/10 min).

Shore A hardness (Shore A hardness) (and Shore D hardness) was measured according to ASTM D2240.

As used herein, Tm or "melting point" (also referred to as melting peak with reference to the shape of the plotted DSC curve) is typically measured by the DSC (differential scanning calorimetry) technique for measuring the melting point or peak value of a polyolefin as described in USP 5,783,638. It should be noted that many blends comprising two or more polyolefins will have more than one melting point or peak, and many individual polyolefins will only comprise one melting point or peak.

An "olefin-based polymer" as used herein is a polymer containing more than 50 mole% polymerized olefin monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Non-limiting examples of the olefin-based polymer include ethylene-based polymers and propylene-based polymers.

A "polymer" is a compound prepared by polymerizing monomers of the same or different type that, in polymerized form, provide multiple and/or repeating "units" or "monomer units" that make up the polymer. Thus, the generic term polymer encompasses the term homopolymer, which is generally used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is generally used to refer to polymers prepared from at least two types of monomers. It also encompasses all forms of copolymers, e.g., random copolymers, block copolymers, and the like. The terms "ethylene/α -olefin polymer" and "propylene/α -olefin polymer" refer to copolymers prepared by polymerizing ethylene or propylene, respectively, with one or more additional polymerizable α -olefin monomers, as described above. It should be noted that although polymers are often referred to as being "made from", "based on" a particular monomer or monomer type, "containing" a particular monomer content, and the like, the term "monomer" should be understood in this context to refer to the polymerized residue of a particular monomer, rather than the unpolymerized species. In general, the polymers referred to herein are based on "units" in the polymerized form of the corresponding monomers.

A "propylene-based polymer" is a polymer containing more than 50 mole% polymerized propylene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer.

Detailed Description

The present disclosure provides a flexible container. In one embodiment, a flexible container includes a first multilayer film and a second multilayer film. Each multilayer film includes a seal layer. The multilayer films are arranged in such a manner that the seal layers are opposed to each other and the second multilayer film is superimposed on the first multilayer film. The multilayer films are sealed along a common peripheral edge. The flexible container includes a fitment having a base. The substrate is formed from a blend of 60 to 90 weight percent of an ethylene/alpha-olefin multi-block copolymer and 40 to 10 weight percent of a high density polyethylene. A flexible container includes a fitment seal comprising the substrate positioned between the multilayer films. The substrate is sealed to each multilayer film along a portion of the common peripheral edge.

1. Accessory

The flexible container of the present invention includes a first multilayer film, a second multilayer film, and a fitment. In one embodiment, the flexible container 8 includes a fitment 10. The fitting 10 has a base 12 and a top 14, as shown in FIG. 1.

The fitting 10 has a base 12 and a top 14, as shown in FIG. 1. The fitment 10 is made of two or more (i.e., blends) polymeric materials. The substrate 12 is made from a polymeric blend composed of an ethylene/alpha-olefin multi-block copolymer and high density polyethylene. The top 14 may include suitable structure (e.g., threads) to connect with the closure.

In one embodiment, the substrate consists of, or is formed of, only a polymeric blend of an ethylene/a-olefin multi-block copolymer and a high density polyethylene.

In one embodiment, the entire fitment 10 (base 12 and top 14) is composed of, or is formed of, only a polymeric blend of an ethylene/a-olefin multi-block copolymer and high density polyethylene.

In one embodiment, the base has walls 15, as shown in FIG. 3. The thickness of the wall 15 is 0.3mm, or 0.4mm, or 0.5mm, or 0.6mm, or 0.7mm, or 0.8mm, or 0.9mm, or 1.0mm to 1.2mm, or 1.5mm, or 1.7mm, or 1.9mm, or 2.0 mm. In another embodiment, the wall 15 is comprised solely of a polymeric blend of an ethylene/a-olefin multi-block copolymer and a high density polyethylene, and has the aforementioned thickness.

The substrate 12 (and optionally the entire fitment 10) is formed from a polymeric blend of an ethylene/alpha-olefin multi-block copolymer and high density polyethylene. The term "ethylene/α -olefin multi-block copolymer" includes ethylene and one or more copolymerizable α -olefin comonomers in polymerized form, characterized in that multiple blocks or segments of two or more polymerized monomer units differ in chemical or physical properties. The term "ethylene/a-olefin multi-block copolymer" includes block copolymers having two blocks (diblock) and more than two blocks (multiblock). The terms "interpolymer" and "copolymer" are used interchangeably herein. When referring to the amount of "ethylene" or "comonomer" in a copolymer, it is understood that this means polymerized units thereof. In some embodiments, the ethylene/a-olefin multi-block copolymer may be represented by the formula:

(AB)_n

wherein n is an integer of at least 1, preferably greater than 1, such as 2,3,4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more, "a" represents a hard block or segment and "B" represents a soft block or segment. Preferably, a and B are linked or covalently bonded in a substantially linear manner, or in a linear manner, relative to a substantially branched or substantially star-shaped manner. In other embodiments, the a and B blocks are randomly distributed along the polymer chain. In other words, block copolymers generally do not have the following structure:

AAA-AA-BBB-BB

in still other embodiments, the block copolymer generally does not have a third type of block comprising a different comonomer. In yet other embodiments, each of block a and block B has a monomer or comonomer substantially randomly distributed within the block. In other words, neither block a nor block B comprises two or more sub-segments (or sub-blocks) of dissimilar compositions, such as end segments, which have a composition that is substantially different from the remainder of the block.

Preferably, ethylene comprises the majority of the mole fraction of the total block copolymer, i.e., ethylene comprises at least 50 mole percent of the total polymer. More preferably, ethylene comprises at least 60 mole%, at least 70 mole%, or at least 80 mole%, wherein substantially the remainder of the entire polymer comprises at least one other comonomer, which is preferably an alpha-olefin having 3 or more carbon atoms. In some embodiments, the ethylene/a-olefin multi-block copolymer may comprise from 50 mol% to 90 mol%, or from 60 mol% to 85 mol%, or from 65 mol% to 80 mol% ethylene. For many ethylene/octene multi-block copolymers, the composition comprises an ethylene content greater than 80 mole% of the total polymer and an octene content from 10 mole% to 15 mole%, or from 15 mole% to 20 mole% of the total polymer.

The ethylene/α -olefin multi-block copolymer comprises various amounts of "hard" segments and "soft" segments. A "hard" segment is a block of polymeric units in which ethylene is present in an amount greater than 90 wt%, or 95 wt%, or greater than 98 wt%, up to 100 wt%, based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 10 wt.%, or 5 wt.%, or less than 2 wt.%, based on the weight of the polymer, and can be as low as zero. In some embodiments, the hard segments comprise all or substantially all units derived from ethylene. A "soft" segment is a block of polymerized units in which the comonomer content (the content of monomers other than ethylene) is greater than 5 wt.%, or greater than 8 wt.%, greater than 10 wt.%, or greater than 15 wt.%, based on the weight of the polymer. In some embodiments, the comonomer content in the soft segment can be greater than 20 wt.%, greater than 25 wt.%, greater than 30 wt.%, greater than 35 wt.%, greater than 40 wt.%, greater than 45 wt.%, greater than 50 wt.%, or greater than 60 wt.%, and can be up to 100 wt.%.

The soft segment can be present in the ethylene/a-olefin multi-block copolymer from 1 wt% to 99 wt%, or from 5 wt% to 95 wt%, from 10 wt% to 90 wt%, from 15 wt% to 85 wt%, from 20 wt% to 80 wt%, from 25 wt% to 75 wt%, from 30 wt% to 70 wt%, from 35 wt% to 65 wt%, from 40 wt% to 60 wt%, or from 45 wt% to 55 wt% of the total weight of the ethylene/a-olefin multi-block copolymer. Conversely, hard segments may be present in similar ranges. The soft segment weight percent and hard segment weight percent can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in U.S. patent No. 7,608,668 entitled "Ethylene/α -Olefin Block interpolymers (Ethylene/α -Olefin Block Inter-polymers)" filed on 3, 15, 2006, in the name of Colin l.p. shann, Lonnie hazlit et al and assigned to Dow Global Technologies Inc (Dow Global Technologies Inc.), the disclosure of which is incorporated herein by reference in its entirety. In particular, the weight percentages of hard and soft segments and the comonomer content can be determined as described in column 57 to column 63 of U.S. 7,608,668.

An ethylene/a-olefin multi-block copolymer is a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") preferably joined (or covalently bonded) in a linear fashion, i.e., a polymer comprising chemically distinguishable units joined end-to-end with respect to polymerized ethylenic functionality rather than joined in a pendant or grafted fashion. In one embodiment, the blocks differ in the following respects: the amount or type of comonomer incorporated, the density, the crystallinity, the crystallite size attributable to a polymer having such composition, the type or degree of stereoisomerism (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching (including long chain branching or hyper-branching), homogeneity or any other chemical or physical property. Compared to prior art block interpolymers, including interpolymers produced by continuous monomer addition, stereo-labile catalysts, or anionic polymerization techniques, the ethylene/α -olefin multiblock copolymers of the present invention are characterized by a unique distribution of polymer polydispersity (PDI or Mw/Mn or MWD), polydispersity block length distribution, and/or polydispersity block number distribution, in one embodiment due to the effect of the shuttling agent used in their preparation in combination with multiple catalysts.

In an embodiment, the ethylene/a-olefin multi-block copolymer is produced in a continuous process and has a polydispersity index (Mw/Mn) from 1.7 to 3.5, or from 1.8 to 3, or from 1.8 to 2.5, or from 1.8 to 2.2. When produced in a batch or semi-batch process, the ethylene/α -olefin multi-block copolymer has a Mw/Mn of 1.0 to 3.5, or 1.3 to 3, or 1.4 to 2.5, or 1.4 to 2.

In addition, the ethylene/α -olefin multi-block copolymer has a fitted Schultz-Flory distribution rather than a Poisson distribution (Po)isson distribution) PDI (or Mw/Mn). The ethylene/alpha-olefin multi-block copolymer of the present invention has both a polydisperse block distribution as well as a polydisperse distribution of block sizes. This allows the formation of polymer products with improved and distinguishable physical properties. Previously described in Potemkin, & ltPhysical review E(Physical Review E)57 (1998)57(6), page 6902-6912 and DobryninJournal of chemistry and physics(J.Chem.Phvs.)107 (1997), pages 9234-9238, modeled and discussed.

In one embodiment, the ethylene/α -olefin multi-block copolymer of the present invention has the most probable distribution of block lengths.

In another embodiment, the ethylene/α -olefin multi-block copolymers of the present disclosure, especially those produced in a continuous solution polymerization reactor, have the most probable distribution of block lengths. In one embodiment of the present disclosure, an ethylene multi-block interpolymer is defined as having:

(A) a Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:

Tm>-2002.9+4538.5(d)-2422.2(d)²or is or

(B) An Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, Δ H, in J/g, and a delta quantity, Δ T, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest crystallization analysis separation ("CRYSTAF") peak, wherein the numerical values of Δ T and Δ H have the following relationships:

for Δ H greater than zero and up to 130J/g, Δ T > -0.1299(Δ H) +62.81

For delta H more than 130J/g, delta T is more than or equal to 48 DEG C

Wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ℃; or

(C) An elastic recovery, Re, in percent measured with a compression molded ethylene/α -olefin interpolymer film at 300% strain and 1 cycle, and having a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/α -olefin interpolymer is substantially free of a crosslinked phase:

re >1481-1629 (d); or

(D) A fraction having a molecular weight that elutes between 40 ℃ and 130 ℃ when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5% higher than a comparable random ethylene interpolymer fraction that elutes between the same temperatures, wherein the comparable random ethylene interpolymer has the same comonomer within 10% of the ethylene/a-olefin interpolymer and has a melt index, density, and molar comonomer content (based on the entire polymer); or

(E) Has a storage modulus G '(25 ℃) at 25 ℃ and a storage modulus G' (100 ℃) at 100 ℃, wherein the ratio of G '(25 ℃) to G' (100 ℃) is in the range of about 1:1 to about 9: 1.

The ethylene/α -olefin multi-block copolymer may also have:

(F) a molecular fraction that elutes between 40 ℃ and 130 ℃ when fractionated using TREF, characterized in that said fraction has a block index of at least 0.5 and up to about 1 and a molecular weight distribution Mw/Mn of greater than about 1.3; or

(G) An average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3.

Suitable monomers for preparing the ethylene/α -olefin multi-block copolymers of the present invention include ethylene and one or more addition polymerizable monomers other than ethylene. Examples of suitable comonomers include linear or branched alpha-olefins of 3 to 30, or 3 to 20, or 4 to 8 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-l-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cyclic olefins of 3 to 30, or 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1, 4,5, 8-dimethylbridge-1, 2,3,4,4a,5,8,8 a-octahydronaphthalene; dienes and polyolefins, such as butadiene, isoprene, 4-methyl-1, 3-pentadiene, 1, 4-pentadiene, 1, 5-hexadiene, 1, 4-hexadiene, 1, 3-octadiene, 1, 4-octadiene, 1, 5-octadiene, 1, 6-octadiene, 1, 7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1, 6-octadiene, 4-ethylidene-8-methyl-1, 7-nonadiene and 5, 9-dimethyl-1, 4, 8-decatriene; and 3-phenylpropylene, 4-phenylpropylene, 1, 2-difluoroethylene, tetrafluoroethylene, and 3,3, 3-trifluoro-1-propene.

In one embodiment, the ethylene/α -olefin multi-block copolymer is styrene-free (i.e., contains no styrene).

Ethylene/a-olefin multi-block copolymers can be produced by a chain shuttling process as described in U.S. Pat. No. 7,858,706, which is incorporated herein by reference. In particular, suitable chain shuttling agents and related information are listed in column 16, line 39 through column 19, line 44. Suitable catalysts are described in column 19, line 45 to column 46, line 19 and suitable cocatalysts are described in column 46, line 20 to column 51, line 28. The method is described throughout the literature, but specifically in column 51, line 29 to column 54, line 56. The method is also described, for example, in the following: U.S. patent No. 7,608,668; US 7,893,166; and US 7,947,793

In one embodiment, the ethylene/α -olefin multi-block copolymer has hard segments and soft segments, is free of styrene, and consists only of (i) ethylene and (ii) C₄-C₈An alpha-olefin comonomer composition and is defined as having:

1.7 to 3.5, at least one melting point, Tm, in degrees celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:

Tm<-2002.9+4538.5(d)-2422.2(d)²，

wherein d is 0.86g/cc, or 0.87g/cc, or 0.88g/cc to 0.89 g/cc;

and is

The Tm is 80 ℃, or 85 ℃, or 90 ℃ to 95 ℃, or 99 ℃, or 100 ℃, or 105 ℃ to 110 ℃, or 115 ℃, or 120 ℃, or 125 ℃.

In an embodiment, the ethylene/a-olefin multi-block copolymer is an ethylene/octene multi-block copolymer (consisting only of ethylene and octene comonomers) and has one, some, any combination, or all of the following properties (i) - (ix):

(i) a melt temperature (Tm) of 80 ℃, or 85 ℃, or 90 ℃ to 95 ℃, or 99 ℃, or 100 ℃, or 105 ℃ to 110 ℃, or 115 ℃, or 120 ℃, or 125 ℃;

(ii) a density of 0.86g/cc, or 0.87g/cc, or 0.88g/cc to 0.89 g/cc;

(iii)50 to 85 wt% soft segment and 40 to 15 wt% hard segment;

(iv) 10 mole%, or 13 mole%, or 14 mole%, or 15 mole% to 16 mole%, or 17 mole%, or 18 mole%, or 19 mole%, or 20 mole% octenes in the soft segment;

(v) 0.5 mol%, or 1.0 mol%, or 2.0 mol%, or 3.0 mol% to 4.0 mol%, or 5 mol%, or 6 mol%, or 7 mol%, or 9 mol% of octenes in the hard segment;

(vi) a Melt Index (MI) of 1 g/10 min, or 2 g/10 min, or 5 g/10 min, or 7 g/10 min to 10 g/10 min, or 15 g/10 min to 20 g/10 min;

(vii) a shore a hardness of 65, or 70, or 71, or 72 to 73, or 74, or 75, or 77, or 79, or 80;

(viii) 300% 300% min at 21 ℃ as measured according to ASTM D1708^·1Elastic recovery (Re) at deformation of 50%, or 60% to 70%, or 80%, or 90%.

(ix) Polydisperse distribution of blocks and polydisperse distribution of block sizes.

In one embodiment, the ethylene/α -olefin multi-block copolymer is an ethylene/octene multi-block copolymer.

The inventive ethylene/a-olefin multi-block copolymers may comprise two or more embodiments disclosed herein.

In one embodiment, the ethylene/octene multi-block copolymer is known under the trade name INFUSE^TMCommercially available from Dow chemical company, Midland, Michigan, USA. In another embodimentIn the examples, the ethylene/octene multi-block copolymer is INFUSE^TM9817。

In one embodiment, the ethylene/octene multi-block copolymer is INFUSE^TM9500。

In one embodiment, the ethylene/octene multi-block copolymer is INFUSE^TM9507。

2. High density polyethylene

The substrate (and optionally the entire fitment) is comprised of a polymeric blend of an ethylene/alpha-olefin multi-block copolymer and a high density polyethylene. "high density polyethylene" (or "HDPE") is an ethylene homopolymer or has at least one C₃-C₁₀An ethylene/alpha-olefin copolymer of an alpha-olefin comonomer and having a density greater than 0.940g/cc, or 0.945g/cc, or 0.950g/cc, or 0.955g/cc to 0.960g/cc, or 0.965g/cc, or 0.970g/cc, or 0.975g/cc, or 0.980 g/cc. Non-limiting examples of suitable comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene. The HDPE comprises at least 50 wt% of units derived from ethylene, i.e. polymerized ethylene, or at least 70 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at least 95 wt% of ethylene in polymerized form. The HDPE may be a unimodal copolymer or a multimodal copolymer. A "unimodal ethylene copolymer" is an ethylene/C copolymer having one distinct peak in Gel Permeation Chromatography (GPC) showing molecular weight distribution₄-C₁₀An alpha-olefin copolymer. A "multimodal ethylene copolymer" is an ethylene/C copolymer having at least two distinct peaks in GPC showing the molecular weight distribution₄-C₁₀An alpha-olefin copolymer. Multimodal includes copolymers having two peaks (bimodal) as well as copolymers having more than two peaks.

In one embodiment, the HDPE has one, some, or all of the following properties: and has one, some, any combination, or all of the following properties (i) - (iv):

(i) a density of 0.950g/cc, or 0.955g/cc, or 0.960g/cc to 0.965g/cc, or 0.970g/cc, or 0.975g/cc, or 0.980 g/cc; and/or

(ii) A Melt Index (MI) of 0.5 g/10 min, or 1.0 g/10 min, or 1.5 g/10 min, or 2.0 g/10 min to 2.5 g/10 min, or 3.0; and/or

(iii) A melt temperature (Tm) of 125 ℃, or 128 ℃, or 130 ℃ to 132 ℃, or 135 ℃, or 137 ℃; and/or

(iv) Bimodal molecular weight distribution.

In an embodiment, the HDPE has a density of 0.955g/cc, or 0.957g/cc, or 0.959g/cc to 0.960g/cc, or 0.963g/cc, or 0.965g/cc and a melt index of 1.0 g/10 minutes, or 1.5 g/10 minutes, or 2.0 g/10 minutes to 2.5 g/10 minutes, or 3.0 g/10 minutes.

Non-limiting examples of suitable commercially available HDPE include, but are not limited to, those available under the trade name CONTINUUM^TMAnd UNIVAL^TMA dow high density polyethylene resin is sold.

HDPE differs from the following types of ethylene-based polymers: LLDPE, m-LLDPE ULDPE, VLDPE, EPE, ethylene/alpha-olefin multi-block copolymers, ethylene plastomers/elastomers and LDPE.

The substrate and/or the entire fitment are comprised of an ethylene/alpha-olefin multi-block copolymer/HDPE polymeric blend. The polymeric blend of ethylene/α -olefin multi-block copolymer and HDPE comprises more than 60 wt%, or 65 wt%, or 70 wt%, or 75 wt% to 80 wt%, or 85 wt%, or 90 wt% of ethylene/α -olefin multi-block copolymer and the inverse amount of HDPE or 40 wt%, or 35 wt%, or 30 wt%, or 25 wt% to 20 wt%, or 15 wt%, or 10 wt% HDPE.

In an embodiment, the entire fitment consists only of the ethylene/α -olefin multi-block copolymer and the HDPE polymeric blend, which includes 70 wt%, or 73 wt%, or 75 wt% to 78 wt%, or 80 wt%, or 83 wt%, or 85 wt%, or 87 wt%, or 90 wt% of the ethylene/α -olefin multi-block copolymer and the inverse amount of HDPE or 30 wt%, or 27 wt%, or 25 wt% to 22 wt%, or 20 wt%, or 17 wt%, or 15 wt%, or 13 wt%, or 10 wt% HDPE.

In an embodiment, the entire fitment consists of only the ethylene/α -olefin multi-block copolymer and the HDPE polymeric blend, which includes 70 wt%, or 73 wt%, or 75 wt% to 78 wt%, or 80 wt%, or 83 wt%, or 85 wt%, or 87 wt%, or 90 wt% of the ethylene/α -olefin multi-block copolymer and the inverse amount of HDPE or 30 wt%, or 27 wt%, or 25 wt% to 22 wt%, or 20 wt%, or 17 wt%, or 15 wt%, or 13 wt%, or 10 wt% HDPE, and the polymeric blend has one, some, or all of the following properties:

(i) shore a hardness (shore D hardness in parentheses) of 80(29), 83(31), 85(33), 87(35), 89(38), 90(39), 91(40), 93(44), 95(46), 97(50), 99(56), or 100 (59); and/or

(ii) An elongation at break of 180%, or 200%, or 220%, or 240%, or 260%, or 280%, or 300%, or 320% to 340%, or 360%, or 380%, or 400%, or 410%; and/or

(iii) A tensile modulus of 50MPa, or 75MPa, or 100MPa, or 125MPa, or 150MPa, or 175MPa, or 200MPa to 225MPa, or 250MPa, or 275 MPa.

Non-limiting examples of ethylene/α -olefin multi-block copolymers and HDPE polymeric blends for use in fittings and related characteristics are set forth in table 1 below.

TABLE 1 polymeric blends with ethylene/alpha-olefin multiblocks

Copolymers and different amounts of HDPE

In parentheses are the reciprocal amounts of the ethylene/alpha-olefin multi-block copolymers

-ethylene/alpha-olefin multiblock copolymer-INFUSE 4817

-HDPE＝DMDC-1250NT 7

3. Multilayer film

The flexible container of the present invention includes a first multilayer film and a second multilayer film. In one embodiment, the flexible container 8 includes a first multilayer film 16 (front film) and a second multilayer film 18 (back film), as shown in fig. 1. The term "first multilayer film" and the term "front film" are used interchangeably. The term "second multilayer film" and the term "back film" are used interchangeably.

The fitment substrate 10 is placed between two opposing multilayer films and then sealed thereto. Each

film

16, 18 has a respective sealant layer comprising an olefin-based polymer.

In an embodiment, each

multilayer film

16, 18 is made of a flexible film having at least one layer, or at least two layers, or at least three layers. The flexible membrane is elastic, flexible, deformable, and pliable. The structure and composition of each

flexible membrane

16, 18 may be the same or different. For example, each

multilayer film

16, 18 may be made from separate webs, each web having a unique structure and/or a unique composition, finish, or printing. Alternatively, each of the

multilayer films

16, 18 may be of the same construction and of the same composition.

The flexible multilayer film is constructed of a polymeric material. Non-limiting examples of suitable polymeric materials include olefinic polymers; a propylene-based polymer; an ethylene-based polymer; polyamides (e.g., nylon), ethylene-acrylic acid or ethylene-methacrylic acid and ionomers thereof with zinc, sodium, lithium, potassium, or magnesium salts; ethylene Vinyl Acetate (EVA) copolymers; and blends thereof. The flexible multilayer film may be printable or compatible to receive pressure sensitive labels or other types of labels for displaying indicia on the flexible container 8.

In an embodiment, a flexible multilayer film is provided and includes at least three layers: (i) an outermost layer, (ii) one or more core layers and (iii) an innermost sealant layer. The outermost layer (i) and the innermost sealing layer (iii) are surface layers with one or more core layers (ii) sandwiched between the surface layers. The outermost layer may comprise (a-i) HDPE, (b-ii) propylene-based polymer or combinations of (a-i) and (b-ii) alone or with other olefinic polymers (e.g., LDPE). Non-limiting examples of suitable propylene-based polymers include propylene homopolymers, random propylene/alpha-olefin copolymers (a majority amount of propylene with less than 10 weight percent ethylene comonomer), and propylene impact copolymers (a heterophasic propylene/ethylene copolymer rubber phase dispersed in a matrix phase).

In the case of one or more core layers (ii), the total number of layers in the multilayer film (16, 18) of the present invention may be three layers (one core layer), or four layers (two core layers), or five layers (three core layers, or six layers (four core layers), or seven layers (five core layers) to eight layers (six core layers), or nine layers (seven core layers), or ten layers (eight core layers), or eleven layers (nine core layers) or more.

Each

multilayer film

16, 18 has a thickness of 75 microns, or 100 microns, or 125 microns, or 150 microns to 200 microns, or 250 microns, or 300 microns, or 350 microns, or 400 microns.

In one embodiment, each

multilayer film

16, 18 is a flexible multilayer film having the same structure and the same composition.

Each

flexible multilayer film

16, 18 may be (i) a coextruded multilayer structure or (ii) a laminate or (iii) a combination of (i) and (ii). In one embodiment, the flexible multilayer film has at least three layers: a sealing layer, an outer layer and a connecting layer therebetween. The tie layer adjoins the sealing layer to the outer layer. The flexible multilayer film may include one or more optional inner layers disposed between the seal layer and the outer layer.

In an embodiment, the flexible multilayer film is a coextruded film having at least two, or three, or four, or five, or six, or seven to eight, or nine, or 10, or 11 or more layers. Some methods of constructing the film are, for example, by cast or blown coextrusion methods, adhesive lamination, extrusion lamination, thermal lamination, and coating, such as vapor deposition. Combinations of these methods are also possible. In addition to the polymeric materials, the film layer may contain additives as are commonly used in the packaging industry, such as stabilizers, slip additives, antiblock additives, processing aids, clarifiers, nucleating agents, pigments or colorants, fillers and reinforcing agents, and the like. It is particularly useful to select additives and polymeric materials having suitable organoleptic and/or optical properties.

In one embodiment, the outermost layer comprises HDPE. In another embodiment, the HDPE is a substantially linear multicomponent ethylene-based copolymer (EPE), such as ELITE supplied by the Dow chemical company^TMAnd (3) resin.

In one embodiment, each core layer comprises one or more linear or substantially linear ethylene-based polymers or block copolymers having a density of 0.908g/cc, or 0.912g/cc, or 0.92g/cc, or 0.921g/cc to 0.925g/cc, or less than 0.93 g/cc. In an embodiment, each of the one or more core layers comprises one or more ethylene/C selected from₃-C₈Alpha-olefin copolymer: linear Low Density Polyethylene (LLDPE), Ultra Low Density Polyethylene (ULDPE), Very Low Density Polyethylene (VLDPE), EPE, Olefin Block Copolymer (OBC), plastomer/elastomer and single site catalyzed linear low density polyethylene (m-LLDPE).

In one embodiment, the seal layer includes one or more ethylenic polymers having a density of 0.86g/cc, or 0.87g/cc, or 0.875g/cc, or 0.88g/cc, or 0.89g/cc to 0.90g/cc, or 0.902g/cc, or 0.91g/cc, or 0.92 g/cc. In another embodiment, the sealing layer comprises one or more ethylene/C selected from EPE, plastomer/elastomer or m-LLDPE₃-C₈An alpha-olefin copolymer.

In one embodiment, the flexible multilayer film is a coextruded film, and the seal layer is composed of an ethylene-based polymer, such as a linear or substantially linear polymer or a single-site catalyzed linear or substantially linear polymer of ethylene and an alpha-olefin comonomer (e.g., 1-butene, 1-hexene, or 1-octene), having a Tm of 55 ℃ to 115 ℃ and a density of 0.865 to 0.925g/cm³Or 0.875 to 0.910g/cm³Or 0.888 to 0.900g/cm³And the outer layer is composed of a polyamide having a Tm of 170 ℃ to 270 ℃.

In one embodiment, the flexible multilayer film is a coextruded and/or laminated film having at least five layers, the coextruded film having a seal layer comprised of an ethylene-based polymer, such as a linear or substantially linear polymer or a single-site catalyzed linear or substantially linear polymer of ethylene and an alpha-olefin comonomer (e.g., 1-butene, 1-hexene, or 1-octene), the ethylene-based polymer having a Tm of from 55 ℃ to 115 ℃ and a density of from 0.865 to 0.925g/cm³Or 0.875 to 0.910g/cm³Or 0.888 to 0.900g/cm³And the outermost layer is composed of a material selected from the group consisting of: hDPE, EPE, LLDPE, OPET (biaxially oriented polyethylene terephthalate), OPP (oriented polypropylene), BOPP (biaxially oriented polypropylene), polyamide and combinations thereof.

In an embodiment, the flexible multilayer film is a coextruded and/or laminated film having at least seven layers. The sealing layer is composed of an ethylene-based polymer, for example a linear or substantially linear polymer or a single-site catalysed linear or substantially linear polymer of ethylene and an alpha-olefin comonomer (e.g. 1-butene, 1-hexene or 1-octene), having a Tm of from 55 ℃ to 115 ℃ and a density of from 0.865 to 0.925g/cm³Or 0.875 to 0.910g/cm³Or 0.888 to 0.900g/cm³. The outer layer is comprised of a material selected from the group consisting of HDPE, EPE, LLDPE, OPET, OPP, BOPP, polyamide, and combinations thereof.

In one embodiment, the flexible multilayer film is a three or more layer coextruded film (or laminate film) wherein all layers are comprised of an ethylene-based polymer. In another embodiment, the flexible multilayer film is a three or more layer coextruded film (or laminate film) wherein each layer is composed of an ethylene-based polymer and (1) the sealing layer is composed of a linear or substantially linear ethylene-based polymer or a single site catalyzed linear or substantially linear polymer of ethylene and an alpha-olefin comonomer (e.g., 1-butene, 1-hexene, or 1-octene), the ethylene-based polymer having a Tm of 55 ℃ to 115 ℃ and a density of 0.865 to 0.925g/cm³Or 0.875 to 0.910g/cm³Or 0.888 to 0.900g/cm³And (2) the outer layer comprises one or more ethylene-based polymers selected from the group consisting of: HDPE, EPE, LLDPE or m-LLDPE, and (3) each of the one or more core layers comprises one or more ethylene/C selected from₃-C₈Alpha-olefin copolymer: linear Low Density Polyethylene (LLDPE), Ultra Low Density Polyethylene (ULDPE), Very Low Density Polyethylene (VLDPE), EPE, Olefin Block Copolymer (OBC), plastomer/elastomer and single site catalyzed linear low density polyethylene (m-LLDPE).

In one embodiment, the flexible multilayer film is a coextruded and/or laminated five layer, or a coextruded (or laminated) seven layer film having at least one layer comprising OPET or OPP.

In one embodiment, the flexible multilayer film is a coextruded (or laminated) five layer \ or coextruded (or laminated) seven layer film having at least one layer comprising a polyamide.

In one embodiment, the flexible multilayer film is a seven-layer coextruded (or laminated) film having a seal layer composed of an ethylene-based polymer of ethylene and an alpha-olefin monomer (e.g., 1-butene, 1-hexene, or 1-octene) having a Tm of 90 ℃ to 106 ℃ or a linear or substantially linear polymer or a single-site catalyzed linear or substantially linear polymer. The outer layer is polyamide with Tm of 170-270 deg.C. The film has an inner layer (first inner layer) composed of a second ethylene-based polymer different from the ethylene-based polymer in the seal layer. The film has an inner layer (second inner layer) composed of the same or different polyamide as the polyamide in the outer layer. The seven-layer film has a thickness of 100 to 250 microns.

4. Fitting seal

The front and

back films

16, 18 are sealed around a common peripheral edge 20. Flexible container 8 includes a fitment seal 22 positioned along a portion of peripheral edge 20. The fitment seal 22 includes a base 12 sandwiched between the front and

rear films

16, 18, (ii) a weld 24 between the front and

base films

16, 12, (iii) a weld 26 between the rear and

base films

18, 12, (iv) a weld 28 between the front and

rear films

16, 18, and (v) in

situ winglets

30 and 32 extending from opposite sides of the base 12, as shown in fig. 3.

The fitment seal 22 is formed by a single stage heat sealing process in which a relatively sealing strip with a concave surface seals the membrane-substrate-membrane sandwich to form in

situ winglets

30, 32 as disclosed in co-pending case ussn 15/276,014 filed on 9, 26/2016. The

welds

24, 26, 28 are formed by means of a heat sealing process that melts or is in a flowable state, (i) a portion of the olefinic polymer in the seal layer of each

respective multilayer film

16, 18 and (ii) a portion of the polymeric blend of the ethylene/a-olefin multi-block copolymer and HDPE is present in the substrate 12. In this manner, weld 24 and weld 26 are comprised of or formed from (i) an ethylene/α -olefin multi-block copolymer and HDPE (from substrate 12), (ii) an olefin-based polymer (from the sealant layer), or (iii) a combination of (i) and (ii). The weld 28 is composed of or formed from an olefin-based polymer from the

multilayer films

16, 18.

The in

situ winglets

30, 32 are formed during the heat sealing process, which forms the fitment seal 22. As used herein, an "in situ winglet" is an extended structure of the substrate 12, an in situ winglet being the polymeric cure of a flowable caulk composed of an ethylene/α -olefin multi-block copolymer (from the substrate 12), the caulk being formed when the substrate is flattened upon heating, and the caulk being cured when the joint gap between the film and the substrate is subsequently pinched and closed. The in situ winglet is comprised of or formed from a blend of (i) an ethylene/alpha-olefin multi-block copolymer and HDPE (from the substrate 12), or (ii) an ethylene/alpha-olefin multi-block copolymer and an olefin-based polymer (from the sealing layer).

The heat and stress of the sealing strip to seal the fitment to the film to make the container is limited. Fittings constructed from low elasticity polyolefins (e.g., only LDPE or only HDPE) can shatter, crack, break, and be unusable. Fittings constructed from polyolefin elastomers (e.g., ENGAGE or VERSIFY elastomers) may exhibit deformation, but may not sufficiently recover or weld shut. A fitting constructed of a crosslinked elastomer (e.g., TPV) may recover completely but not seal adequately and does not form a hermetic seal. Applicants have unexpectedly found that a fitment constructed from the polymeric blend of the present invention of an ethylene/a-olefin multi-block copolymer and HDPE recovers (springs back) and does not seal to itself and seals the fitment to the film of a container using a counter-sealing bar heat sealing technique. In particular, the substrate 12 comprised of the inventive blend of ethylene/α -olefin multi-block copolymer and HDPE having an elastic recovery of 50% to 90% is flexible enough to seal against cracking, cracking or breaking, and elastic enough to spring back, rebound and open into a sealed oval cross-sectional shape.

In an embodiment, the length B (fig. 3) of each in situ winglet is 0.5mm, or 1.0mm, or 2.0mm, or 3.0mm, or 4.0mm, or 5.0 mm.

In one embodiment, the base 12 has walls 15. The thickness of the wall 15 is 0.3mm, or 0.4mm, or 0.5mm, or 0.6mm, or 0.7mm, or 0.8mm, or 0.9mm, or 1.0mm to 1.2mm, or 1.5mm, or 1.7mm, or 1.9mm, or 2.0 mm.

In one embodiment, substrate 12 has an oval shaped cross-section. Non-limiting examples of elliptical shapes include circular, substantially circular, lenticular, and biconvex.

In one embodiment, the elliptical cross-section has a major axis C and a minor axis D, as shown in FIG. 3. The ratio of the length of the major axis to the length of the minor axis (in mm) is 4:1, or 3:1, or 2:1 to 1: 1.

In one embodiment, the fitting seal 22 is a hermetic seal.

In one embodiment, the fitting seal 22 is a hard seal. As used herein, a "hard seal" is a hot seal that cannot be manually separated without breaking the membrane. Hard seals are different from frangible seals. As used herein, a "frangible seal" is a hot seal that cannot be separated (or peeled) manually without breaking the film. Generally, the frangible seal is designed to be separated or opened by applying finger or hand pressure to the seal. The hard seal is designed to remain intact upon application of finger or hand pressure to the seal.

5. Flexible container

The flexible container of the invention can be a box-shaped bag, a pillow-shaped bag, a spout k sealing bag and a spout side-mounted gusset bag. The location of the fitment (spout or valve or other) mounted into the container may be any location, for example in sealing the bottom gusset to the front panel, a seal being present between the two membranes, i.e. on the top, side or even the bottom. In other words, fitment seal 22 may be located or otherwise formed anywhere on a flexible container where two films meet and are heat sealed together. Non-limiting examples of suitable locations for fitment seal 22 include the top, bottom, sides, corners, gusseted regions of the flexible container.

The flexible container of the present invention may be formed with or without a handle.

In an embodiment, the flexible container is a Stand Up Pouch (SUP) as shown in fig. 1 and 4. SUP comprises a gusset 34. The gussets 34 are attached to or extend from the lower portion of the front membrane 16 and/or the lower portion of the rear membrane 18. The gusset 34 includes a gusset film 36 and a gusset edge 38. The gussets 34 may be formed by heat sealing, welding (ultrasonic or high frequency or radio frequency), adhesive bonding, and combinations thereof. The gusset 34,

membranes

16, 18 and fitment seal 22 define a closed and hermetically sealed chamber for holding a flowable substance, such as a liquid.

The gusset 34 is made of a flexible polymeric material. In one embodiment, the gussets 34 are made of a multi-layer film having the same structure and composition as the front and

back films

16, 18. The corner supports 34 provide (1) structural integrity to support the SUP and its contents from leakage, and (2) stability of the SUP upright (i.e., based on a supporting surface, such as a horizontal surface or a substantially horizontal surface) from tipping over. In this sense, the bag is a "stand-up" bag.

In one embodiment, the gusset 34 is an extension of one or both of the

multilayer films

16, 18. The folding procedure forms the gussets 34 from one or both of the

films

16, 18.

The gusset edge 38 defines a SUP-facing surface. The cover surface can have a variety of shapes. Non-limiting examples of suitable shapes for the cover surface include circular, square, rectangular, triangular, oval, elliptical, eye-shaped, and tear-drop shaped. In another embodiment, the shape of the cover surface is elliptical.

In an embodiment, the flexible container comprises a closure. Non-limiting examples of suitable fittings and closures include screw caps, flip top caps, snap caps, liquid or beverage dispensing fittings (stopcocks or thumb plungers), cooler fitting connectors, tamper-proof pour spouts, vertical screw caps, horizontal screw caps, sterile caps, vitop presses, push taps, stem caps, cono fitting connectors, and other types of removable (and optionally reclosable) closures. The closure and/or fitting may or may not include a gasket.

In one embodiment, the flexible container includes a closure that is a screw cap 40 as shown in fig. 1A and 1B. The threads 17 on the fitting top 14 and the reciprocal threads 42 in the screw cap 40 engage each other to provide an air-tight seal between the fitting 10 and the screw cap 40 when the screw cap is fully threaded onto the fitting 10.

In one embodiment, the flexible container 8 has a volume of 0.25 liters (L), or 0.5L, or 0.75L, or 1.0L, or 1.5L, or 2.5L, or 3L, or 3.5L, or 4.0L, or 4.5L, or 5.0L to 6.0L, or 7.0L, or 8.0L, or 9.0L, or 10.0L, or 20L, or 30L.

In one embodiment, the flexible container of the present invention is made from 90 to 100 weight percent of an ethylene-based polymer-the

films

16, 18 and the gussets 34 are comprised of a flexible multilayer film having layer materials selected from the group consisting of ethylene-based polymers, such as LLDPE, LDPE, HDPE and combinations thereof, and the fitment 10 is comprised of a polymeric blend of an ethylene/α -olefin multi-block copolymer and HDPE. Weight% is based on the total weight of the flexible container (without contents). Flexible containers made from 90 to 100 weight percent ethylene-based polymer are advantageous because they can be easily recycled.

The flexible containers of the present invention are suitable for storing flowable materials including, but not limited to, liquid foods (e.g., beverages), oils, coatings, greases, chemicals, suspensions of solids in liquids, and solid particulate materials (powders, grains, granular solids). Non-limiting examples of suitable liquids include liquid personal care products such as shampoos, conditioners, liquid soaps, lotions, gels, creams, balms, and sunscreens. Other suitable liquids include home care/cleaning products and automotive care products. Other liquids include liquid foods such as dressings (ketchup, mustard, mayonnaise) and baby food.

The flexible container of the present invention is suitable for storing flowable substances which have a relatively high viscosity and require application of a squeezing force to the container for discharge. Non-limiting examples of such squeezable and flowable materials include fats, butter, margarine, soap, shampoo, animal feed, sauce, and baby food.

Examples of the present disclosure are provided as examples and not limitations.

Examples of the invention

A flexible multilayer film having the structure shown in table 2 below was used in the present example.

1. Multilayer film

TABLE 2 composition of Flexible multilayer film (film 1)

Laminated multilayer film

2. Accessory

Nine Comparative Samples (CS) and four Inventive Examples (IE) were prepared. The dimensions of each fitting are the same, with only the material being changed in all fittings. The CS fitting is made up of 100% by weight of INFUSE 9817. The inventive assembly consists of 70 wt% of INFUSE9817 and 30 wt% of DMDC-1250NT 7 HDPE. The bottom wall thickness of each fitting was 0.8mm, and the base inner diameter was 12.5mm and the base outer diameter was 14.1 mm.

The materials and compositions used for the fittings are shown in table 3 below.

TABLE 3 Accessory materials

3. Conditions of treatment

Each fitting was placed between two opposing films of film 1 (from table 2) with the sealing layers facing each other.

Each fitment-film configuration was heat sealed using opposing sealing bars having a concave surface between a flat front surface and a flat concave surface as set forth in co-pending application ussn 15/276,014 filed on 26/9/2016 (conditions below).

TABLE 4 processing conditions for mounting fittings

The heat sealing procedure results in a flexible container, which is a Stand Up Pouch (SUP), as shown in fig. 1-5.

4. Leak test

The Lippke test evaluates SUP for additional seal integrity. The Lippke test perforates the flexible container with a needle and pressurizes air to 150mbar according to the conditions described in table 5 below. After 60 seconds, the pressure difference was recorded. If the flexible container does not fail, the pressure will remain unchanged. The flexible container sample was immersed in the water tank to observe the presence of cracks or failed bubbles. The Lippke test determines whether the failure is from a triple seal or from a different source, such as a bad fitting-closure joint.

Leak testing of flexible containers was performed under the following parameters.

TABLE 5 Lippke test procedure

The flexible container is subjected to an internal pressure of 150 mbar. The test needs to wait 60 seconds to complete. The pressure drop was measured for 60 seconds. The flexible container was then submerged in water and the spout/lid joint was observed to monitor for the presence of bubble formation. A higher pressure drop value indicates a higher leakage in the package.

TABLE 6 Lippke test results of SUP

Sample (I)	Pressure drop (mbar) after 60 seconds	Note book
			CS 1	20.6	High leakage at spout/lid joint
CS 2	146.7	Nozzle orificeComplete leakage of lid
			CS
3	46.9	High leakage at spout/lid joint
			CS 4	46.1	High leakage at spout/lid joint
CS 5	60.1	High leakage at spout/lid joint
			CS 6	9.1	High leakage at spout/lid joint
CS 7	146.6	Spout/lid total leakage
			CS
8	18.6	High leakage at spout/lid joint
			CS 9	64.2	High leakage at spout/lid joint
IE 1	4.6	No visual leakage at spout/lid joint
			IE 2	4.6	No visual leakage at spout/lid joint
IE
	3	5.5	No visual leakage at spout/lid joint
IE 4				4.6	No visual leakage at spout/lid joint

The test pressure for all samples in table 6 was 150 mbar.

Table 6 shows that fittings made with the polymeric blends of the present invention of 60 to 90 wt% ethylene/α -olefin multi-block copolymer (especially ethylene/octene multi-block copolymer) and 40 to 10 wt% HDPE exhibit less deformation during the heat sealing process and also exhibit improved spring back and recovery after heat sealing compared to fittings composed of 100 wt% ethylene/α -olefin multi-block copolymer.

The inventive fittings made with the polymeric blend of ethylene/alpha-olefin multi-block copolymer and HDPE recovered to a more adequate degree (after heat sealing) than fittings made with 100 wt% ethylene/alpha-olefin multi-block copolymer. The inventive fitting reverts to a circular or substantially circular cross-sectional shape after heat sealing. The circular cross-sectional post-seal shape of the inventive fitting resulted in better fitting-to-closure sealing as evidenced by the lower Lippke test pressure drop when compared to fittings made from 100 wt.% ethylene/alpha-olefin multi-block copolymer.

It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.

Claims

1. A flexible container, comprising:

a first multilayer film and a second multilayer film, each multilayer film comprising a seal layer composed of an olefinic polymer, the two multilayer films being arranged such that the seal layers are opposed to each other and the second multilayer film is superimposed on the first multilayer film, the two multilayer films being sealed along a common peripheral edge;

a fitment comprising a substrate comprising a polymeric blend of 60 to 90 weight percent of an ethylene/a-olefin multi-block copolymer and 40 to 10 weight percent of a high density polyethylene HDPE, wherein the polymeric blend has an elastic recovery of 50 to 90 percent as measured according to ASTM D1708;

an in-situ formed winglet extending from an opposite side of the substrate, the winglet comprised of an ethylene/a-olefin multi-block copolymer, HDPE, and an olefinic polymer from the sealing layer;

a fitment seal comprising the substrate located between the two multilayer films, and the substrate is sealed to each multilayer film at a portion of the common peripheral edge; and

the flexible container exhibits a pressure drop of less than 6mbr as measured according to the Lippke test.

2. The flexible container of claim 1 wherein the HDPE has a density of from 0.955g/cc to 0.965 g/cc.

3. The flexible container of claim 2 wherein the HDPE has a melt index of 1.0 g/10 min to 3.0 g/10 min.

4. The flexible container of claim 3 wherein the HDPE is a bimodal HDPE.

5. The flexible container of claim 1 wherein the base has a wall thickness of 0.3mm to 2.0 mm.

6. The flexible container of claim 1 wherein the polymeric blend has a shore a hardness of 80 to 100.

7. The flexible container of claim 1 wherein the polymeric blend has an elongation at break of 180% to 410%.

8. The flexible container of claim 1 wherein the polymeric blend has a tensile modulus of 50MPa to 275 MPa.

9. The flexible container of claim 1 wherein the fitment comprises a top extending from the base, the base and the top being comprised of the polymeric blend.

10. The flexible container of claim 9 wherein the flexible container is a stand-up pouch.

11. The flexible container of claim 1 including a closure secured to the fitment.